Formal Semisynthesis of Demethylgorgosterol Utilizing a Stereoselective Intermolecular Cyclopropanation Reaction

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Rosenbaum , N , Schmidt , L , Mohr , F , Fuhr , O , Nieger , M & Bräse , S 2021 , ' Formal Semisynthesis of Demethylgorgosterol Utilizing a Stereoselective Intermolecular Cyclopropanation Reaction ' , European Journal of Organic Chemistry , vol. 2021 , no. 10 , pp. 1568-1574 . https://doi.org/10.1002/ejoc.202100035

Title: Formal Semisynthesis of Demethylgorgosterol Utilizing a Stereoselective Intermolecular Cyclopropanation Reaction
Author: Rosenbaum, Nicolai; Schmidt, Lisa; Mohr, Florian; Fuhr, Olaf; Nieger, Martin; Bräse, Stefan
Contributor organization: Department of Chemistry
Date: 2021-03-12
Language: eng
Number of pages: 7
Belongs to series: European Journal of Organic Chemistry
ISSN: 1434-193X
DOI: https://doi.org/10.1002/ejoc.202100035
URI: http://hdl.handle.net/10138/328116
Abstract: In this study, we report a convenient and high yielding formal semisynthesis of demethylgorgosterol, a marine steroid with an intriguing sidechain containing a cyclopropane unit. This was achieved through the synthesis of an advanced ketone intermediate. The synthetic route features a total of ten steps, starting from commercially available stigmasterol, with an overall yield of 27 %. The key step was a stereoselective intermolecular cyclopropanation reaction. This reaction proceeded in 82 % yield, the resulting cyclopropane carboxylic ester shows a trans/cis ratio of 89 : 11, with a diastereomeric ratio for the trans-diastereomers of >99 : 1. A reduction/oxidation sequence afforded the corresponding aldehyde, which was used in a Grignard reaction. A final oxidation step then yielded the desired ketone. This novel route presents a platform to further investigate the medicinal applications of gorgosterol-type steroids and to fully understand their role in coral symbiosis.
Subject: Cyclopropanation
Gorgosterol
Steroids
Stereoselective synthesis
Ruthenium
116 Chemical sciences
Peer reviewed: Yes
Rights: cc_by
Usage restriction: openAccess
Self-archived version: publishedVersion


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